Ureidoalkylphosphonates

ABSTRACT

NOVEL UREIDOALKYULPHOSPHONATES, METHODS FOR THEIR PREPARATION AS WELL AS FOR THEIR USE IN PREPARING DURABLE, FLAMEPROOF FINISHES FOR TEXTILES ARE DISCLOSED THESE UREIDOALKYLPHOSPHONATES ARE FOUND TO BE LOW IN COST, READILY PREPARED AND OF MINIMAL TOXICITY.

United States Patent O 3,763,281 UREIDOALKYLPHOSPHONATES Edward D. Weil, Hastings-on-Hudson, N.Y., assignor to Stauffer Chemical Company, New York, N.Y. N Drawing. Filed June 26, 1970, Ser. No. 50,304 Int. Cl. C07f 9/40; D06c 27/00 U.S. Cl. 260-932 Claims ABSTRACT OF THE DISCLOSURE Novel ureidoalkylphosphonates, methods for their preparation as well as for their use in preparing durable, fiameproof finishes for textiles are disclosed These ureidoalkylphosphonates are found to be low in cost, readily prepared and of minimal toxicity.

BACKGROUND OF THE INVENTION The condensation products of formaldehyde with ureas are Well known substances widely employed to prepare thermoset resins which find a multitude of uses as adhesives, coatings, binders, and as finishes for paper, wood and textiles.

Urea-formaldehyde resins are in themselves rather incombustible. However, when they are applied to combustible substrates such as paper, cloth, wood, or the like, the resulting combination is often highly combustible. 'It has been known that the addition of such phosphorus containing additives as phosphoric acid, ammonium phosphate and the like markedly reduces the flammability of the products resulting from the combination of ureaformaldehyde resins with combustible substrates. However, such additives are readily removed upon even a minimal leaching with water. Thus, for uses where resistance to water is necessary as in coatings, apparel fabrics, paper, wood, plywood, and the like, these additives do not provide sufficiently durable, flame-retarding compositions.

The literature describes previous attempts to prepare urea derivatives having organic phosphorus groups attached to the nitrogen atoms of the urea, e.g. U.S. Pat. No. 3,393,253. However, the resulting compounds have direct phosphorus-to-nitrogen bonds which results in their having less than the desired degree of hydrolytic stability. Moreover, such compounds must be made through the use of the dangerously unstable N-chlorourea intermediate.

It is, therefore, the prime object of this invention to provide stable, urea derivatives having organically bound phosphorus substituted thereon. It is a further object to provide phosphorus substituted urea derivatives useful for conducting condensation or co-condensation reactions which yield aminoplastic resins having utility as durable flame retardant coatings, binders, adhesives, and finishes for various substrates including textiles and paper as Well as for use as molding resins. It is still another object to make available new processes for preparing these phoshporus containing urea derivatives. Various other objects and advantages of this invention will be apparent from a reading of the disclosure which follows hereinafter.

TECHNICAL DISCLOSURE OF THE INVENTION It has now been discovered that a novel class of inexpensive, non-toxic ureidoalkylphosphonates'may be conveniently prepared, these derivatives being capable of providing durable flame retardant finishes for a variety of flammable substrates and particularly for textiles.

The novel compounds of this invention correspond to the structural formula:

where R R R and R are selected from the group consisting of: hydrogen; hydroxymethyl; C -C alkoxymethyl; methylene conjoining two urea nuclei having substituents as here defined and a phosphonate group Z where Z corresponds to the formula:

in which n is an integer having a value of from 0 to l and R is selected from the group consisting of C -C alkyl, allyl, C C 2-chloroalkyl and C C Z-hydroxyalkyl groups; where R and R can be conjointly equal t0 CH CH -CH2CH2CH2, -CH2N(C1C12 and groups; where R and R can be conjointly equal to a OHCI-I group in which the free valences of each carbon atom in said group comprise the R and R groups of a second urea nucleus corresponding to the structure:

with the proviso that at least one and no more than three of said R R R and R groups are Z groups and that at least one of said R R R and R groups is selected from the group consisting of hydrogen, hydroxymethyl, C C alkoxymethyl, and -CHOHCHOH groups.

The above described ureidoalkylphosphonates may be prepared by means of various reaction procedures depending upon their precise composition. Thus, for example, where n is the above given structural formula is to be 0, the urea intermediate used as starting material should contain the R R R and R groups which are desired in the end product except that in the position(s) in the end product which is(are) to be substituted with a Z group, the urea intermediate will have a hydroxymethyl, i.e. a methylol group. The selected urea intermediate is then caused to react in the liquid phase at 0 to C. with at least one molar equivalent of a trialkyl phosphite having the formula P(OR where R is defined above, until substantially one molar equivalent of an R OH alkanol by-product is released or substantially no further trivalent phosphorus remains detectable.

Surprisingly, this process yields the phosphonate structure -NCH P(0R instead of the phosphite strucv 3 ture NCH OP(OR which would be expected to be produced under these conditions by means of a simple transesterification. This procedure will, hereinafter, be referred to as Process No. 1.

Alternatively, if the starting urea intermediate in Process No. 1 contains a C -C alkoxymethyl rather than a Z group, it can be reacted, in the liquid phase at to 180 C., with at least one molar equivalent of a dialkyl phosphonate having the formula until substantially one equivalent of an alkanol has been evolved or until no further HP compound can be detected in the reaction mixture. This procedure will, hereinafter, be referred to as Process No. 1a. It is to be noted that Processes Nos. 1 and la may be conducted with a mixture of two or more urea intermediates and/ or trialkyl phosphites and/or dialkyl phosphonates.

In still another reaction procedure, where n in the ureidoalkylphosphonate is to be 1, the urea compound used as the starting intermediate should contain the R R R and R groups which are desired in the end product except that where there is to be a Z group in the end product, the starting urea intermediate should contain a hydroxymethyl, ie a methylol, group or a C C alkoxymethyl group. The selected urea intermediate is then caused to react, in the liquid phase, at 20-180 C. with at least one molar equivalent of a dialkylphosphonate having the formula preferably in the presence of an acid catalyst such, for example, as sulfuric acid, p-toluenesulfonic acid, phosphoric acid, or the like, until substantially one molar equivalent of water, in the case of a starting urea having a methylol methyl group, or one molar equivalent of alkanol, in the case of a starting urea having a C C alkoxymethyl group, has been evolved. The latter procedure is, hereinafter, to be referred to as Process No. 2. It is to be noted that it may be conducted with a mixture of two or more urea intermediates and/or dialkylphosphonates.

There is another useful process, hereinafter referred to as Process No. 3, for preparing those compositions of this invention wherein the R R R and R groups are to be selected from the group consisting of C -C alkoxymethyl, methylene conjoining two urea nuclei or where R and R are conjointly groups in which the free valences of the last named radical are joined to a second urea nucleus, and where at least one of R R R or R is a phosphonate group Z as defined hereinabove wherein n equals zero. This additional method consists of reacting a correspondingly substituted urea intermediate, having a C -C alkoxymethyl group at the site to be occupiedby Z, with a dialkyl phosphorochloridite of the type (R O) PCl or with an amount of trialkyl phosphite of the formula (R O) P along with PCI;, equivalent to the amount of the phosphorochlorodite. The trialkyl phosphite is first preferably added to the urea intermediate followed by the addition of the P'Cl The reaction is carried out at a temperature of about 20 to 180 C. and preferably at about 0 to 120 C. and for a period of from about one minute to about 50; hours depending on the temperature. In general, the reaction mixture is maintained at the reaction temperature until. trivalent phosphorus is no longer detectable whereupon it is stripped of the alkyl chloride by-product.

This method is especially suitable, for example, for making co positions of the ype 'OH2-CH2 from bis(methoxymethyl)ethyleneurea,

from bis(methoxymethyl)propyleneurea and 0. II II NCH2P(OR5)2 from bis(methoxymethyl)uron.

Where any of the R R R or R groups in the final ureidoalkylphosphonate are to be hydroxymethyl, C C alkoxymethyl,

CHCH there are two procedures which can be used for preparing such products. Thus, either such group(s) can be present in the initial urea intermediate prior to the formation of the phosphonate group Z, or, alternatively, the urea intermediate can contain hydrogen in place of the ultimately desired R R R or R groups and the Z group(s) are then introduced by the use of either reaction process No. 1, 1a, or 2 as described above. In addition, the de sired R R2,. R and R groups can also be introduced by methods which in themselves are well known inv the art. For example, (a) where introduction of hydroxyemthyl groups is desired, an appropriate substitute urea intermediate is reacted with formaldehyde under alkaline conditions; (b) where introduction of C C alkoxymethyl groups is desired, an appropriately substitute urea intermediate is reacted with formaldehyde under alkaline conditions followed by reaction of the resulting product with a C -C alkanol under acid conditions; (c) where introduction of --CHOHCHOH groups is desired, an appropriately substituted urea intermediate is reacted with glyoxal; (d) where introduction of -CH OCH groups is desired, the intermediate is reacted with at least; two molar equivalents of formaldehyde under alkaline conditions whereupon the resulting product is reacted with methanol under acid conditions; (e) where introduction of r groups is desired, an appropriately substituted intermediate is reacted with two equivalents of formaldehyde and one equivalent of H N(C -C alkyl); and (f) where introduction of groups is desired, an approximately substituted urea intermediate is reacted with /2 molar equivalent of glyoxal under acid conditions.

Suitable urea intermediates for use in the process of this invention include, for example, mono-, diand trimethylolurea; monoand dimethylol ethyleneureas or propyleneureas; mono-, di-, triand tetramethylolglyoxaldurein; and the alkoxy, especially the. C -C alkyl ethers,

of all of these ureas, bis(methoxymethyl)uron; bis(methoxymethyl)methyltriazone.

Suitable trialkyl phosphites include trimethyl, triethyl, tripropyl, tributyl, triamyl, trioctyl and tridodecyl phosphites; methyl didecyl phosphite; triallyl phosphite; methyl diallyl phosphite; tris-Z-hydroxyethyl phosphite and tris-2-chloroethyl phosphite etc.

Suitable dialkyl phosphonates (phosphites) include dimethyl, diethyl, dipropyl, diallyl, methyl allyl, dibutyl, didodecyl, di-2-chloroethyl, di-Z-hydroxyethyl, and di-2- hydroxypropyl phosphonate, etc.

Suitable dialkylphosphorochloridites include dimethyl, diethyl, dipropyl, dibutyl, diallyl, bis(2-chloroethyl), dioctyl, methyl ethyl and methyl propyl phosphoroehloridite.

Suitable hydroxymethylphosphonates include dimethyl,

' diethylfdiallyl, dipropyl, didodecyl, di-2-chloroethyl, and

di-Z-hydroxypropylphosphonate, etc.

Reaction conditions for processes Nos. 1, la and 2, as described above, can entail operation at atmospheric pressure, at sub-atmospheric pressure which would aid in stripping off the alcohol or water by-product or at superatmospheric pressure. The reactants may be brought together without a solvent or one can utilize a solvent which will not interfere with the reaction such, for example, as an alcohol, a hydrocarbon, an ether, an ester, a chlorinated hydrocarbon, or a nitrile.

Process No. 1 proceeds without a catalyst although it can be accelerated by adding a catalytically effective concentration of a base such as sodium methylate or sodium carbonate. Process 1a generally does not require the use of any catalyst. On the other hand, process 2 proceeds best with an effective concentration of an acid catalyst such, for example, as sulfuric acid, hydrochloric acid, organic sulfonic acids, acidic clays, acidic ion exchange resins, trifluoroacetic acid, trichloroacetic acid, fiuoroboric acid and the like. It should be noted, at this point that the above described reaction procedures for preparing these novel derivatives will often yield mixtures of two or more ureidoalkylphosphonates.

The novel ureidoalkylphosphonates of this invention are, in general, viscous liquids or low melting thermoplastic resinous solids. Usually they are soluble in water and in alcohols. In some cases, especially where R R R and R as defined above, are not hydroxymethyl, they are soluble in less polar organic solvents such as toluene, xylene, mineral spirits, esters, such as ethyl acetate, ketones such as acetone or isophorone and chlorinated hydrocarbons such as chloroform and are, thus, compatible with organic solvent-based coating and ink formulations as well as with non-aqueous textile finishing formulations.

The ureidoalkylphosphonates of this invention where at least one of the R R R or R groups is a methylol or a C -C alkoxymethyl group and where at least one additional R R R or R group is hydrogen, methylol or C C alkoxymethyl are self-curable forming crosslinked resins under acid catalyzed conditions. Suitable acid catalysts for this purpose include sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, trichloroacetic acid, trifluoroacetic acid, alkyl acid phosphates and the like. Furthermore, all of the ureidoalkylphosphonates of this invention are co-curable with aminoplast-forrning co-reactants, under acid catalyzed conditions, forming flame retardant, crosslinked resin products having durably bonded phosphorus, useful as textile finishes, coatings, laminates, adhesives and moldings.

Suitable aminoplast-forming co-reactants include ureaformaldehyde condensation products, melamine-formaldehyde condensation products, and urea-glyoxal-formaldehyde condensation products.

The products of the invention can also be co-cured With phenol-formaldehyde or with furfural condensation products or with alkyd resins, or with thermosetting acrylic resins so as to form flame retardant, crosslinked resins having durably bound phosphorus, useful in textile finishes, coatings, laminates, adhesives and moldings.

As has already been noted, hereinabove, the ureidoalkylphosphonates of this invention provide excellent results when utilized as fiameproofing finishes for flammable substrates such as paper and for both natural and synthetic textile materials. It is also noteworthy to point out that the textile finishes derived from these derivatives may also be characterized as durable press finishes since they permit the textiles to which they have been applied to retain their original shape and remain wrinkle-free after being laundered without any need for having them ironed.

Textiles may be treated with the derivatives of the invention while the latter are dissolved in aqueous medium. And, where R R R and R as defined above, are not hydroxymethyl, they may be applied while in the form of hydrocarbon, organic solvent solutions utilizing such essentially nonpolar solvents as methylene chloride, ethylene dichloride, trichloroethene, perchloroethylene, etc. and mixtures thereof. This ability to employ the ureidoalkylphosphonates of this invention in organic solvent media, the use of which is becoming increasingly more important in the textile finishing art, represents a distinct advantage with respect to the flame retardant, phosphorus containing urea derivatives of the prior art which generally lacked organic solvent solubility.

The solutions, either aqueous or organic solvent, containing one or more of the ureidoalkylphosphonate derivatives of this invention, may be applied to textiles by the use of any desired procedure. It is merely necessary to have the ureidoalkylphosphonate absorbed throughout the mass of the textile and/ or to apply it to at least one surface thereof by means of any convenient procedure. Thus, they may be applied by being sprayed onto one or both surfaces of the textile or, as is more frequently the case, the textile may be passed or padded through the solution while the latter is being held in a tank or other suitable container. Such a process is commonly referred to as a padding technique with the solution being referred to as a padding bath or padding solution.

The concentration of the ureidoalkylphosphonate within the padding bath, or other applicable solution, will be dependent upon a number of factors including the nature of the fibers which comprise the textile, the Weight and weave of the textile, the degree of fiameproofing that is desired in the finished textile, as well as other technical or economic considerations known and understood by those skilled in the art. However, it is generally desirable that the padding bath should contain from about 5 to by weight, of one or more of the ureidoalkylphosphonate; the latter concentration being sufiicient to deposit a finish upon the textile which will contain from about 5 to 75 by weight, of the textile, of the ureidoalkylphosphonate which, in turn, will provide the thus treated textile with about 0.2 to 7.5%, by weight, of the textile, of phosphorus. Again, it is to be stressed that the latter limits are merely illustrative and may be varied so as to provide a textile finish having and desired degree of flame retardancy.

Subsequent to their deposition upon and/or their absorption by a textile, the ureidoalkylphosphonates contained within the padding solution may be cured, or crosslinked, so as to yield a highly durable, fire retardant finish. This curing operation may be accomplished by air drying the treated fabric for a period of from about one to 10 days at ambient temperature, or, a more rapid cure may be affected by the application of heat at temperatures of up to about 200 C. Under the latter conditions, a curing time as short as only about one second may be required. Additional control of the curing rate may be achieved by the optional presence in the padding solution of pH controlling substances such as acid releasing salts which accelerate or catalyze the rate of cure or basic substances which will, on the other hand, retard the cure rate.

Rate retarding substances, include, for example, alkali metal hydroxides, such as sodium hydroxide; and alkali metal bicarbonates and carbonates such as sodium bicarbonate and sodium carbonate. Cure accelerators, or catalysts, are exemplified by ammonium, alkaline earth and transition metal salts such as ammonium chloride, magnesium chloride, zinc chloride and zinc nitrate; amine hydrochlorides such as diethanolamine hydrochloride triethyleneamine hydrochloride; and, organic and inorganic acids such as acetic, oxalic, maleic, malic, citric, trichloroacetic, hydrochloric and phosphoric acids and alkyl acid phosphates. These optional curing rate retarders and accelerators may, respectively, be used alone or in combination with one another in a concentration which is suflicient to attain the cure rate desired by the practitioner.

Another class of optional adjuvants which may be included Within the solutions containing the ureidoalkylphosphonate derivatives of this invention, when the latter are being used for the preparation of flame retardant textile finishes, are various so-called co-reactants. These coreactants are materials which will undergo a reaction with the ureidoalkylphosphonate and which are used for various purposes such as to control the crosslink density of the finish, to improve the hand and durability of the fin ished textile :as well as its durability, flame retardance, durable press, laundering and crease resistance properties. Particularly useful as co-reactants are aminoplastic-forming reagents such, for example, as urea; condensation products of ureaformaldehyde, urea-glyoxal or ureaglyoxal-formaldehyde; melamine; melamine-formaldehyde condensation products; N-methylolated O-alkyl carbamates; ammonia, and formaldehyde. Each of the above described co-reactants are capable of use either alone or admixed with one another. It is to be understood, that the use, in the above given list, of the term urea is meant to include Within its scope various cyclic ureas such, for example, as ethyleneurea, propyleneurea, uron, triazones, glyoxaldiurein and isocyanuric acid.

Other suitable co-reactants include formamide, acetamide, propionamide, dialkoxyphosphonopropionamide or the N-rnethylol derivatives thereof, tetrakis(hydroxymethyl) phosphonium chloride or hydroxide, trimethylol phosphine, aminated phosphonitrilic chloride, phosphoric triamide and thermal condensation products thereof, ammonium phosphates, glycol such as the phosphorus-containing glycols and the hydroxyalkyl esters of all phosphorus acids. Particularly useful as co-reactants are the novel triazinylaminophosphonates disclosed in copending application Ser. No. 50,364 filed June 26, 1970, now U.S. Pat. No. 3,755,532.

In general, the ureidoalkylphosphonate finishing reagents of this invention can be made to condense during the above described curing process with co-reactant compounds having either OH, NH, or N--CH OCH groups and the proper selection of such co-reactants in order to achieve a desired modification of crosslink density, crease resistance, durable press, and flame retardant properties will be evident to those skilled in the art. Some specific co-reactants which may be named are:

dimethylolmelamine;

trimethylolmelamine;

dimethylol dihydroxyethyleneurea; trismethoxymethylmelamine;

dimethyloluron;

dimethylolethyleneurea; dimethylolpropyleneurea;

N,N-dimethylol methyl carbamate; N,N-dimethylol 2-hydroxyethylcarbamate; N,N-dirnethylol ethyl carbamate; N,N-dimethylol methoxyethylcarbamate; methylolurea;

dimethylolurea;

partially methylated pentamethylolmelamine; tetramethylolglyoxaldiurein;

N-methylol-Z- dimethoxyphosphono propionamide; and, N-methylolacrylamide.

Various other classes of optional adjuvants may also be present in the textile finishing solutions of this invention. Thus, the padding bath containing the ureidoalkylphosphonates of this invention and the textile finishes derived, therefrom, may contain other ingredients in order to modify the finish in accordance with practices known to those skilled in the art of textile finishings.

For example, these other ingredients may include hand modifiers such as polyethylene emulsions, long chain fatty amides, parafiin Waxes, long chain quaternary ammonium salts, and the like; auxiliary flame retardants such as chloroparaffins, chlorinated polyethylene, polyvinyl chloride, polyvinylidene chloride, homoor copolymers of vinyl phosphonates and antimony compounds such as antimony oxide, antimony phosphate, and the like; soil release, anti-soiling agents and water and oil-repellents such as polyfluoroalkyl compounds, silicones, acrylic acid copolymers, and the like; abrasion resistance agents such as polyacrylates, polyurethanes, and the like; colorants and color modifying agents such as dyes, pigments, bleaches, anti-fading agents, ultraviolet screening agents and the like; anti-static agents such as quaternary ammonium compounds; humectants; bonding agents; antimicrobial agents which Will supplement the inherent rot-resistance and antimicrobial action of the ureidoalkylphosphonate containing finishes of this invention; and pH modifying agents. The padding bath may also contain adjuvants intended to directly facilitate the padding operation per se, such as emulsifying and Wetting agents, swelling agents, and buffers.

Although the novel finishes of this invention are most notably effective on cellulosic textiles, nonetheless all types of textiles may be treated by means of the process of this invention so as to provide them with durable, fire retardant finishes. Thus, one may treat textiles derived from natural fibers such as cotton, wool, silk, sisal, jute, hemp and linen and from synthetic fibers including nylon and other polyamides; polyolefins such as polypropylene; polyesters such as polyethylene terephthalate; cellulosics such as rayon, cellulose acetate and tri-acetate; fiber glass; acrylics and modacrylics, i.e. fibers based on acrylonitrile copolymers; saran fibers, i.e. fibers based on vinylidene chloride copolymers; nytril fibers, i.e. fibers based on vinylidene dinitrile copolymers; rubber based fibers; spandex fibers, i.e. fibers based on a segmented polyurethane; vinal fibers, i.e. fibers based on vinyl alcohol copolymers; vinyon fibers, i.e. fibers based on vinyl chloride copolymers; and, metallic fibers. Textiles derived from blends of any of the above listed natural and/ or synthetic fibers may also be treated by means of the process of this invention.

As used in this disclosure, the term textile or textiles is meant to encompass woven or knitted fabrics as well as non-woven fabrics which consist of continuous or discontinuous fi-bers bonded so as to form a fabric by mechanical entanglement, thermal interfiber bonding or by use of adhesive or bonding substances. Such non-Woven fabrics may contain a certain percentage of wood pulp as well as conventional textile fibers in which case part of the bonding process is achieved by means of hydrogen bonding between the cellulosic pulp fibers. In non-Woven fabrics, the finishing agents of this invention can serve not only as flame retardant finishes but can also contribute to the interfiber bonding mechanism by serving as all or part of the adhesive or bonding resin component. This dual role can also be played by the finishing agents of this invention in fabric laminates where the finishing agent can at the same time serve as the interlaminar bonding agent and as the flame retardant. In both of these systems, i.e. non-Woven fabrics and laminated fabrics, the finishing agents of this invention can also be blended with the usual bonding agents such, for example, as acrylic emulsion polymers, vinyl acetate, homoand copolymer emulsions, styrene butadiene rubber emulsions, urethane resin emulsions, polyvinylchloride emulsions, polyvinylchloride-acrylate emulsions, polyacrylates modified by vinyl carboxylic acid comonomers and the like.

In addition to being used for the preparation of fire retardant textile finishes, the novel ureidoalkylphosphonates of: the invention may also be used in various other applications in which their flame retardant properties are advantageous. These include their being cured or co-cured with co-reactants as named above into thermoset resins which may be employed for the preparation of molded objects and coatings or for laminating or impregnating paper and wood, or as adhesives. In molding applications, fillers such as wood flour, clays, mica and the like are often advantageously employed. The resins of the invention in either uncured or thermoset form may also be used as flame retardant additives for other resins.

The following examples further illustrate the embodiment of this invention. In these examples all parts given are by weight unless otherwise noted.

Example I This example illustrates the preparation of one of the novel ureidoalkylphosphonates of this invention by means of the reaction of trimethyl phosphite with dimethylolurea.

A mixture of 24 g. (0.2 mole) of commercial dimethylolurea and 100 g. of redistilled trimethyl phosphite was stirred and heated at 100 C. over a 1 hour period with substantially all of the thoretical amount of methanol being removed with a fractionating column. The reaction mixture was then heated to 133 C., subsequently cooled and stiripped free of excess trimethyl phosphite to a pot temperature of 137 and final vacuum of 1.5 mm. The residual product comprised 55 g. (92% yield) of a viscous, nearly colorless syrup which was soluble in water and chloroform. The infrared spectrum showed NH (3320), C=O (1675-1690), NH (1568), P =O (1230- 1260 CID-1). The nuclear magnetic reasonance spectrum showed two types of CH OP groups and P-CH groups in an incompletely resolved multiplet at 3.7 p.p.m. as well as NH at 6.6, the area ratio of CH to NH corresponding to the theoretical for a urea substituted by two groups. The presence of two types of CHgOP groups suggests that both N,N' and N,N-disubstituted structures are present as follows:

and

O O CHA C sh NHaCN Analysis.-Calcd. for C H '0 P N (percent): P, 20.4; N, 9.2. Found (percent): P, 19.5; N, 9.4.

A small amount of -NH-CH O structures may also be present, indicated by an N.M.R. signal at 4.36

p.p.m.

Example 2 This example illustrates the preparation of one of the novel ureidoalkylphosphonates of this invention by means of the reaction of triethyl phosphite with dimethylolurea.

In a similar manner to Example 1, hereinabove, dimethylolurea was reacted with triethyl phosphite. Theproduct was a pale yellow syrup the N.M.R. spectrum of which showed NH, CH and CH bands in an area ratio of 1.7:12: 12. Theoretical for urea substituted by two group, 2: 12:12.

Analysis.Calcd. for C H O P N (percent): P, 14.9; N, 6.7. Found (percent): P, 13.5; N, 5.9.

Example 3 This example illustrates the use of one of the novel ureidoalkylphosphonates of this invention for the flameproofing of textiles:

A padding bath was formulated as follows:

Parts The product of Example 1, hereinabove 9.2

Hexamethoxymethylelamine 12.0

Zinc nitrate (catalyst) 0.2 Octylphenoxypolyethoxyethanol (a non-ionic surfractant) 0.02

Plus sufficient water to provide total of 50 parts by weight.

A sample of 8 ounce cotton cloth was treated with this solution at a 70%, by weight, wet add-on and a 25%, by weight, dry add-on. After curing at C. for 5 minutes, it was found to be self-extinguishing when ignited and useful self-extinguishing properties persisted after laundering. The cloth contained 1.4%, by weight, of phosphorus after hot water washing and 0.7%, by weight, of phosphorus after soda ash-soap laundering at 100 C.

Example 4 This example illustrates the preparation of the monomethylol derivatives of the ureidoalkylphosphonates whose respective preparation is illustrated in Examples 1 and 2 hereinabove.

'(A) To a solution of 18 parts of the product of Example 1 in 12 parts of water therein was added 4.9 parts of 37% aqueous formaldehyde. The pH was adjusted to 9.4- 9.5 and held for 1 hr. at this level by the periodic addition of aqueous NaOH. Finally, the pH was adjusted to 6.9 by the dropwise addition of concentrated hydrochoric acid. The solution was then made up to a total of 100 parts by weight by adding water.

(B) In a similar manner, 21.7 parts of the product of Example 2 was reacted with formaldehyde in a 2% excess over equimolar.

It was then made up to a total of 65.5 parts with additional water. In both instances, the reaction of the major part of the formaldehyde was established by assaying the finished solution for unreacted formaldehyde.

Example 5 This example illustrates the use, for the fiameproofing of textiles, of the monomethylated derivative whose preparation was described in part (A) of Example 4, hereinabove.

A padding bath was prepared by blending the solution of the monomethylated product of Example 2, whose preparation was described in Part A of Example 4, with 4.75 parts of pentamethylolmelamine, 0.95 parts of urea, 0.4 parts of ammonium chloride as a catalyst and 0.2 parts of octylphenoxypolyethoxyethanol. The bath was then made up to a total of 95 parts by adding water. Eight ounce cotton cloth was padded in this solution, dried, cured at C. for 10 minutes and washed. It was found to be self-extinguishing when ignited in air.

Examples 6 15 These examples are illustrative of the preparation of additional species of the novel ureidoalkylphosphonates of this invention.

Following the procedure of Example 1, hereinabove, various ureidoalkylphosphonates were prepared by means of the respective reactions between a number of different urea intermediates and phosphorus containing reactants. The following table describes the thus prepared ureidoalkylphosphonates and provides all of the information relating to the process conditions and reagents utilized for their preparation.

diluted with 50 cc. of toluene. After a three hour addition period, the mixture was left standing overnight. Mercurometric assay showed that about 0.1 mole of trimethyl phosphite remained unreacted. Stripping to 70 C./0.1 mm. removed the methyl chloride, the toluene and the excess trimethyl phosphite, leaving behind 265 g. of the desired product having the formula:

where R R R and R are selected from the group consisting of hydrogen, hydroxymethyl, C C alkoxymethyl, methylene cojoining two urea nuclei having substituents as here defined, and a phosphonate group Z where Z corresponds to the formula:

in which n is an integer having a value of from 0 to 1 and R is selected from the group consisting of C C alkyl, allyl, C C 2-chloroalkyl, and C -C hydroxyalkyl with the proviso that two of said R R R and R groups are Z groups and that at least one of said R R R and R groups is selected from the group consisting of hydrogen, hydroxymethyl and alkoxymethyl.

2. The ureidoalkylphosphonate corresponding to the formula:

3. The ureidoalkylphosphonate corresponding to the formula:

4. The ureidoalkylphosphonate corresponding to the formula:

5. The ureidoalkylphosphonate corresponding to the formula:

0 O CHzl (OCH2H5)2 NHZCN CH2? (0 CH2H5)2 References Cited UNITED STATES PATENTS 9/1963 Haabein 260-938 X OTHER REFERENCES Ivanov et al.: Index Chemicus, vol. 33, No. 7, May 19, 1969, No. 112548.

Cason et al.: J. Org. Chem., vol. 23 (1958), pp. 1302- 5.

LEWIS GOTTS, Primary Examiner A. H. UTTO, Assistant Examiner US. Cl. X.R.

117-136; 2528.1; 260239 BC, 244 R, 248 NS, 248 CS, 251, 309.7, 93 8, 969

Patent. No. 5,765,28l Dated October 2, 1973 Inventor(s) Edward D, Weil It: is certified that error appears in the above-identified patent and that said Letteri Patent are hereby corrected as shox-m below:

Column 1, line 58, delete the word "phoshporus" and in its place insert -phosphorus- Q Column 5, second formula, first line after the letter "P" delete "(OC and in its place insert ---(OR Column 7, line 21 end of line, after "fin" delete and in its place insert a dash f Column 9, line 61, delete the following "(percent)" Column 9, line 62, delete the following "(percent)" Column 10, line 4, delete the following "(percent)" Column 10, line 5, delete the following "(percent)" Column 10, line 14, delete the word "Hexamethoxymethylelamine" and in its place insert the word '--Hexamethoxymethylmelamine-- Column 10, line 1-7, delete the portion of word'"fractant" and in its place insert --factant-- Column 11 and 12, Example. 13100 9, under "Proposed Structure of Principal Product" N on left is .single bonded to CH this should read --CI-I V I I Column 15, in the Table, Example 14, under "Proposed Structure of Principal Product" C is single bonded to "NCH P(OCH which is single bonded from the P to an O this should be double bonded to, an 00 v I 7 9 Column 16, line l9, first P in formula is single bonded to O- should be double bonded to 0.,

Signed and sealed this 5th day of March 1974;

(SEAL) Attest:

EDWARD M.FLETCHER,JR. M R DANN Attesting Officer 1 V Commissioner of Patents Patent No. 3,765,2fil Dated October 2, 1975 lrwentoi-(sfl EdwardD. Weil It is certified 1112.; error appears in the above-identified patent and that said Letter? Patent are hereby corrected as shox-m below:

l Column 1, line 5'3], delete the word "phoshporus" and in its place insert --phosphorus- Column 5, second formula, first line after the letter "P" delete "(OC and in its place insert --(OR Column '7, line 21 end of line, after "fin" delete and in its place insert a dash I Column 9, line 61, delete the following "(percent) Column 9, line 62, delete the following "(percent) Column 10, line 4, delete the following "(percent) Column 10, line 5, delete the following "(percent)" Column 10, line 14, delete the word "Hexamethoxymethylelamine" and in its place insert the 'word '--Hexamethoxymethylmelamine Column 10, line 17, delete the portion of word "fractant" and in its place insert --factant Column ll and 12, Example. No. 9, under 'Proposed Structure of Principal Product" N on left is single bonded to CH this should read --CI-I v Column 15, in the Table, Example 1 under Proposed Structure of Principal Product" C is single bonded to "NC'H P(OCH which is single bonded from the P to an O this should be double bonded to an O0 4 Column 16, line 19, first P in formula is single bonded to O should be double bonded to O,

Signed and sealed this 5th day of March 1974 (SEAL) Attest:

EDWARD M.FLETCHER,JR. MARSHALL DANN Attesting Officer Commissioner of Patents 

